Superparamagnetic silica nanoparticles with immobilized metal affinity ligands for protein adsorption

Superparamagnetic silica-coated magnetite (Fe₃O₄) nanoparticles with immobilized metal affinity ligands were prepared for protein adsorption. First, magnetite nanoparticles were synthesized by co-precipitating Fe²⁺ and Fe³⁺ in an ammonia solution. Then silica was coated on the Fe₃O₄ nanoparticles using a sol–gel method to obtain magnetic silica nanoparticles. The condensation product of 3-Glycidoxypropyltrimethoxysilane (GLYMO) and iminodiacetic acid (IDA) was immobilized on them and after charged with Cu²⁺, the magnetic silica nanoparticles with immobilized Cu²⁺ were applied for the adsorption of bovine serum albumin (BSA). Scanning electron micrograph showed that the magnetic silica nanoparticles with an average size of 190 nm were well dispersed without aggregation. X-ray diffraction showed the spinel structure for the magnetite particles coated with silica. Magnetic measurement revealed the magnetic silica nanoparticles were superparamagnetic and the saturation magnetization was about 15.0 emu/g. Protein adsorption results showed that the nanoparticles had high adsorption capacity for BSA (73 mg/g) and low nonspecific adsorption. The regeneration of these nanoparticles was also studied.     

Evidence for magnetic interactions among magnetite nanoparticles dispersed in photoreticulated PEGDA-600 matrix

Magnetite nanoparticles having mean diameter of about 8 nm have been prepared by a thermo-chemical route. Different amounts (5 and 10% wt) of a stable dispersion of magnetite nanoparticles in n-hexane were added to polyethylene glycol diacrylate (PEGDA-600) oligomer containing 2% wt of radicalic photoinitiator. The homogenized mixture was poured on a silica glass substrate and the resulting film was photoreticulated in N₂ atmosphere using a UV lamp. As a result, a polymer-based magnetic nanocomposite was obtained, where the magnetic nanoparticles are dispersed in the diamagnetic matrix, as checked by SEM. Morphology, composition, and size of as-prepared nanoparticles were checked by SEM and X-ray diffraction. The magnetic properties of magnetite nanoparticles prior to and after inclusion in the polymeric matrix have been studied by means of an alternating-gradient magnetometer (T interval: 10–300 K, H_MAX: 18 kOe). FC-ZFC curves were obtained in the same temperature interval. The results show that the nanocomposites cannot be simply described as containing superparamagnetic particles undergoing an anisotropy-driven blocking and that collective magnetic interactions play a non-negligible role. Low-temperature hysteretic properties indicate that the polymeric matrix affects the effective anisotropy of magnetite nanoparticles. Dispersion of magnetite NPs in PEGDA has non-trivial consequences on their magnetic properties.     

Study of structural and magnetic properties of superparamagnetic Fe3O4/SiO2 core–shell nanocomposites synthesized with hydrophilic citrate-modified Fe3O4 seeds via a sol–gel approach

This paper describes a simple way for the coating of magnetite nanoparticles (MNPs) with amorphous silica. First, MNPs were synthesized by controlled co-precipitation technique under N₂ gas and then their surface was modified with trisodium citrate in order to achieve particles with improved dispersibility. Afterward, magnetite-silica core/shell nanocomposites were prepared by a sol–gel approach, using magnetic fluid including electrostatically stabilized MNPs as seeds. The prepared samples were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, zeta potential analysis and vibrating sample magnetometer (VSM) in order to study their structural and magnetic properties. FT-IR and XRD results imply that resultant nanocomposites are consisted of two compounds; Fe₃O₄ and SiO₂ and TEM images confirm formation of their core/shell structure. TEM images also show increase in silica shell thickness from ∼5 to ∼24 nm with increase in amount of tetraethyl orthosilicate (TEOS) used during the coating process from 0.1 to 0.3 mL. Magnetic studies indicate that Fe₃O₄ nanoparticles remain superparamagnetic after coating with silica although their M_s values are significantly less than pristine MNPs. These core/shell nanocomposites offer a high potential for different biomedical applications due to having superparamagnetic property of magnetite and unique properties of silica.     

Magnetodielectric effect in composites of nanodimensional glass and CuO nanoparticles

Nanocomposites comprising CuO particles of average diameter 21 nm coated with 5 nm silica glass containing iron ions were synthesized by a chemical route. An ion exchange reaction at the nanoglass/CuO interface produced iron-doped CuO with copper ion vacancies within the nanoparticles. Room temperature ferromagnetic-like behavior was observed in the nanocomposites. This was ascribed to uncompensated spins contributed by Fe ions with associated copper ion vacancies. A rather high value of magnetodielectric parameter in the range 16–26% depending on the measuring frequency was exhibited by these nanocomposites at a magnetic field of 10 KOe. This was caused by a magnetoresistance of 33% in the iron doped CuO nanoparticles. The experimental results were fitted to the Maxwell–Wagner Capacitor model developed by Catalan. These materials will be suited for magnetic sensor applications.     

Application of silica–magnetite nanocomposites to the isolation of ultrapure plasmid DNA from bacterial cells

The aim of this study was to develop a simple and rapid method for purification of ultrapure plasmid DNA with high yields from bacterial cultures. Nanosized superparamagnetic nanoparticles (Fe₃O₄) were prepared by chemical precipitation method using Fe²⁺, Fe³⁺ salt, and ammonium hydroxide under a nitrogen atmosphere. Silica–magnetite nanocomposites were prepared by the method of acid hydrolysis of tetraethoxysilane (TEOS) to coat the silica onto magnetite nanoparticles. DNA was adsorbed to the support under high salt conditions, and recovered directly in water for immediate downstream application, without the need for precipitation. We demonstrated that a useful plasmid, pRSETB-EGFP, encoding for the green fluorescent protein with T7 promoter, could be amplified in Escherichia coli of DE3 strain. Up to approximately 43 μg of high-purity (A₂₆₀/A₂₈₀ ratio=1.75) plasmid DNA was isolated from 3 ml of an overnight bacterial culture. The eluted plasmid DNA was used directly for restriction enzyme digestion, bacterial cell transformation and polymerase chain reaction (PCR) amplification with success. The protocol, starting from the preparation of bacterial lysate and ending with purified plasmid takes less than 8 min. The silica–magnetite nanocomposites deliver significant time-savings, overall higher yields, lower RNA contamination, and better PCR amplification compared to commercial available silica-based and other methods.     

Fabrication and characterization of superparamagnetic and thermoresponsive hydrogels based on oleic-acid-coated Fe3O4 nanoparticles, hexa(ethylene glycol) methyl ether methacrylate and 2-(acetoacetoxy)ethyl methacrylate

Stimuli-responsive hydrogel nanocomposites comprised of swollen polymer networks, in which magnetic nanoparticles are embedded, are a relatively new class of “smart” soft materials presenting a significant impact on various technological and biomedical applications. A novel approach for the fabrication of hydrogel nanocomposites exhibiting temperature- and magneto-responsive behavior involves the random copolymerization of hexa(ethylene glycol) methyl ether methacrylate (HEGMA, hydrophilic, thermoresponsive) and 2-(acetoacetoxy)ethyl methacrylate (AEMA, hydrophobic, metal-chelating) in the presence of preformed oleic-acid-coated magnetite nanoparticles (OA·Fe₃O₄). In total, two series of hydrogel nanocomposites have been prepared in two different solvent systems: ethyl acetate (series A) and tetrahydrofuran (series B). The degrees of swelling (DSs) of all conetworks were determined in organic and in aqueous media. The nanocrystalline phase adopted by the embedded magnetic nanoparticles was investigated by X-ray diffraction (XRD) spectroscopy. The obtained diffraction patterns indicated the presence of magnetite (Fe₃O₄). Deswelling kinetic studies that were carried out at ∼60 °C in water demonstrated the thermoresponsive properties of the hydrogel nanocomposites, attributed to the presence of the hexaethylene glycol side chains within the conetworks. Moreover, thermal gravimetric analysis (TGA) measurements showed that these materials exhibited superior thermal stability compared to the pristine hydrogels. Further to the characterization of compositional and thermal properties, the assessment of magnetic characteristics by vibrational sample magnetometry (VSM) disclosed superparamagnetic behavior. The tunable superparamagnetic behavior exhibited by these materials depending on the amount of magnetic nanoparticles incorporated within the networks combined with their thermoresponsive properties may allow for their future exploitation in the biomedical field.     

The Study of Aggregation Processes in Colloidal Solutions of Magnetite–Silica Nanoparticles by NMR Relaxometry,AFM, and UV–Vis-Spectroscopy

Colloidal solutions of magnetic nanoparticles were studied as a promising magnetic resonance imaging (MRI) contrast agent. The problem of aggregative stability of solutions is considered. Sol-gel synthesis of magnetite colloidal solutions stabilized by silica is described. Transmittance spectra were measured to analyze sedimentation of nanoparticles in magnetite–silica solutions of different compositions and concentrations. It is shown that the synthesized nanoparticles can be used as MRI contrast agents. The surface morphology and particle size of Fe₃O₄/SiO₂ layers were estimated by atomic force mictroscopy (AFM) technique. The mechanism of magnetic-field-induced aggregation of Fe₃O₄/SiO₂ nanoparticles into chain-like and fractal structures is described.     

Magnetic nanocomposite spinel and FeCo core-shell and mesoporous systems

The fabrication of condensed silica and mesoporous silica coated spinel CoFe₂O₄ and FeCo alloy magnetic nanocomposites are reported. The encapsulation of well-defined 5 nm thick uniform silica layer on CoFe₂O₄ magnetic nanoparticles was performed. The formation of mesopores in the shell was a consequence of removal of organic group of the precursor through annealing. The NiO nanoparticles were loaded into the mesoporous silica. The mesoporous silica shells leads to a larger coercivity than that of pure CoFe₂O₄ magnetic nanoparticles due to the decrease of interparticle interactions and magneto-elastic anisotropy. In addition, the FeCo nanoparticles were coated by condensed and mesoporous silica. The condensed silica can protect the reactive FeCo alloy from oxidation up to 300 °C. However, saturation magnetization of FeCo nanoparticles coated by silica after 400 °C annealing is dramatically decreased due to the oxidation of the FeCo core. The mesoporous silica coated magnetic nanostructure loaded with NiO as a final product could be used in the field of biomedical applications.     

Preparation and rheological studies of uncoated and PVA-coated magnetite nanofluid

Experimental studies of rheological behavior of uncoated magnetite nanoparticles (MNPs)U and polyvinyl alcohol (PVA) coated magnetite nanoparticles (MNPs)C were performed. A Co-precipitation technique under N₂ gas was used to prevent undesirable critical oxidation of Fe²⁺. The results showed that smaller particles can be synthesized in both cases by decreasing the NaOH concentration which in our case this corresponded to 35 nm and 7 nm using 0.9 M NaOH at 750 rpm for (MNPs)U and (MNPs)C. The stable magnetic fluid contained well-dispersed Fe₃O₄/PVA nanocomposites which indicated fast magnetic response. The rheological measurement of magnetic fluid indicated an apparent viscosity range (0.1–1.2) pa s at constant shear rate of 20 s⁻¹ with a minimum value in the case of (MNPs)U at 0 T and a maximum value for (MNPs)C at 0.5 T. Also, as the shear rate increased from 20 s⁻¹ to 150 s⁻¹ at constant magnetic field, the apparent viscosity also decreased correspondingly. The water-based ferrofluid exhibited the non-Newtonian behavior of shear thinning under magnetic field.     

Synthesis and characterization of silica-coated nanoparticles of magnetite

Magnetic nanoparticles coated with silica have been subjected of extensive, and, in many aspects, also intensive investigations because of their potential application in different technological fields, particularly in biomedicine. This work was conceived and is being carried out in two main parts: (1) synthesis of the ferrimagnetic nanoparticles, specifically magnetite, and (2) coating these particles with tetraethyl orthosilicate (TEOS). The nanosized magnetite sample was prepared by the reduction–precipitation and the nanomagnetite particles were coated by the sol-gel method, based on the hydrolysis of tetraethyl orthosilicate (TEOS). The so obtained materials were characterized with powder X-ray diffraction (XRD), FTIR spectroscopy, saturation magnetization measurements, and ⁵⁷Fe Mössbauer spectroscopy at room temperature.     

Surface functionalization of silica-coated magnetic nanoparticles for covalent attachment of cholesterol oxidase

A systematic approach towards the fabrication of highly functionalized silica shell magnetic nanoparticles, presently used for enzyme immobilization, is herein fully presented. The synthesis of bare maghemite (γ-Fe₂O₃) nanoparticles was accomplished by thermal co-precipitation of iron ions in ammonia alkaline solution at harsh reaction conditions, respectively. Primary surface engineering of maghemite nanoparticles was successfully performed by the proper deposition of silica onto nanoparticles surface under strictly regulated reaction conditions. Next, the secondary surface functionalization of the particles was achieved by coating the particles with organosilane followed by glutaraldehyde activation in order to enhance protein immobilization. Covalent immobilization of cholesterol oxidase was attempted afterwards. The structural and magnetic properties of magnetic silica nanocomposites were characterized by TEM and vibrating sample magnetometer (VSM) instruments. X-ray diffraction measurements confirmed the spinel structure and average size of uncoated maghemite nanoparticles to be around 20 nm in diameter. SEM-EDS spectra indicated a strong signal for Si, implying the coating procedure of silica onto the particles surface to be successfully accomplished. Fourier transform infrared (FT-IR) spectra analysis confirmed the binding of amino silane molecules onto the surface of the maghemite nanoparticles mediated Si-O-Si chemical bonds. Compared to the free enzyme, the covalently bound cholesterol oxidase retained 50% of its activity. Binding of enzyme onto chemically modified magnetic nanoparticles via glutaraldehyde activation is a promising method for developing biosensing components in biomedicine.     

Oleic acid coating on the monodisperse magnetite nanoparticles

Monodisperse magnetite nanoparticles provide a more factual model to study the interface interactions between the surfactants and magnetic nanoparticles. Monodisperse magnetite nanoparticles of 7 and 19 nm coated with oleic acid (OA) were prepared by the seed-mediated high temperature thermal decomposition of iron(III) acetylacetonate (Fe(acac)₃) precursor method. Fourier transform infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS) reveal that the OA molecules were adsorbed on the magnetic nanoparticles by chemisorption way. Analyses of transmission electron microscopy (TEM) shows the OA provided the particles with better isolation and dispersibility. Thermogravimetric analysis (TGA) measurement results suggest that there were two kinds of different binding energies between the OA molecules and the magnetic nanoparticles. The cover density of OA molecules on the particle surface was significantly various with the size of magnetite nanoparticles. Magnetic measurements of the magnetite nanoparticles show the surface coating reduced the interactions among the nanoparticles.     

Log-pile photonic crystal of CdS–polymer nanocomposites fabricated by combination of two-photon polymerization and in situ synthesis

A log-pile photonic crystal of CdS nanoparticles–polymer nanocomposites was successfully fabricated by a novel method combining the two-photon polymerization technique and in situ synthesis of CdS nanoparticles in a polymer matrix. The photonic band gap of the three-dimensional (3D) log-pile photonic crystal is confirmed and becomes more effective for CdS nanoparticles–polymer nanocomposites than polymer doped with Cd²⁺ ions, because the nanocomposites possess a higher refractive index than the polymer. The proposed concept in the new fabrication method for a 3D microstructure of polymer nanocomposites should be of critical importance in providing a general methodology for functionalization of materials via functional nanocomposites used in the field of laser microstructure fabrication. PACS 42.70.Qs; 78.66.Sq; 81.40.Tv; 82.35.Np; 82.50.Pt     

A Theoretical and Experimental Study of NMR Contrasting Properties of Nanocomposites Based on Ferric Oxides Stabilized by Arabinogalactan Matrix

Nuclear magnetic resonance relaxation properties of aqueous solution containing nanocomposites based on magnetite and maghemite nanoparticles stabilized by arabinogalactan obtained from Baikal larch (Larix sibirica) wood matrix were investigated. The relaxation properties of the solutions, namely, viscosity dependences of T ₁ and T ₂ and magnetic field dependence of T ₁, were studied experimentally. Two models of the nanocomposite granular structure corresponding to two limiting cases of ferromagnetic material distribution over the arabinogalactan matrix were considered. The first one assumes a homogeneous distribution of magnetite and maghemite nanoparticles over the spherical arabinogalactan matrix, while the second one considers a single hard ferromagnetic core at the center of the spherical arabinogalactan matrix. Theoretical fitting of the experimental results within these models was performed.     

Properties of three-dimensional composites based on opal matrices and magnetic nanoparticles

Three-dimensional nanocomposites consisting of an opal matrix and a metal have been prepared by the interaction of salts and oxides of different elements (Ni, Co, Fe, etc.) embedded in an opal matrix with isopropanol in the range of supercritical state parameters of the alcohol. According to X-ray powder diffraction analysis and transmission electron microscopy data, the composites consist of an X-ray amorphous opal matrix with pores filled by nanoparticles of Co (or CoO _x ), metallic Ni, or Fe₃O₄ with a magnetite structure of various morphology. The sizes of the nanoparticles do not exceed the diameter of the pores in the opal matrix. A complex investigation of the nanocomposites has been performed using the electron magnetic resonance and vibrating magnetometry methods. All the studied samples at room temperature exhibit a ferromagnetic behavior. The coercive force of the samples lies in the range from 150 Oe for iron-containing nanocomposites to 565 Oe for cobalt-containing nanocomposites.     

Preparation and Fluoroimmunoassay Application of New Red-Region Fluorescent Silica Nanoparticles

This is the first report on the preparation and utilization of a novel red-region fluorescent dye (tetracarboxy aluminum phthalocyanine) doped silica nanoparticles. In these nanoparticles, the tetracarboxy aluminum phthalocyanine molecules were covalently bound to silica matrix to protect the dye leaking from nanoparticles in bio-applications. The surface of the nanoparticles was modified by amino groups and easily bioconjugated with goat anti-human IgG antibody. By employing these nanoparticles as fluorescent probe, a sensitive fluoroimmunoassay method has been developed for the determination of trace level of human IgG. The calibration graph for human IgG was linear over the range of 0–500 ng mL⁻¹ with a detection limit of 1.6 ng mL⁻¹. Compared with the corresponding system using free AlC₄Pc as a probe for determining human IgG, the sensitivity of the proposed system was notably increased. The method was applied to the analysis of human IgG in human sera with satisfactory results.     

Synthesis and surface modification of hydrophobic magnetite to processible magnetite@silica-propylamine

Hydrophobic magnetite nanoparticles with a narrow size distribution were prepared by thermal decomposition of Fe(CO)₅ in octyl ether solution of oleic acid and by consecutive aeration. The nanoparticles were converted into magnetite core/silica shell (magnetite@silica) structured particles with hydrophilic and processible aminopropyl groups on their surfaces.     

Superparamagnetism of magnetite particles in C<Subscript>60</Subscript> fullerite powder

A new magnetic material, C₆₀ fullerite powder doped by magnetite (Fe₃O₄) nanoparticles, is obtained by heating a mixture of fullerite and iron(III) acetylacetonate. It is shown that the material offers superparamagnetic properties. Surface bonding between the nanoparticles and the fullerite is established.     

Synthesis and Thermal Behavior of Silica‐Graft‐Polypropylene Nanocomposites Studied by Step‐Scan DSC and TGA

Silica graft poly(propylene) (silica‐g‐PP) nanocomposites were successfully prepared by radical grafting copolymerization and ring‐opening reaction. Their thermal properties were studied by step‐scan differential scanning calorimetry (SDSC) and thermogravimetric analysis (TGA). The exothermic peaks in the IsoK baseline (C_p,IsoK, nonreversing signal) of SDSC reveal that PP and silica‐g‐PP nanocomposites undergo melting‐recrystallization‐remelting during heating. The peak temperatures of recrystallization and remelting shift upward with the existence of nanoparticles in the PP matrix. The thermal degradation kinetics of silica‐g‐PP nanocomposites were investigated using nonisothermal TGA and the Flynn‐Wall‐Ozawa method. The results indicate that the thermal stability was significantly improved with increasing silica content, mainly because of the physical‐chemical adsorption of the volatile degradation products on the nanoparticles that delays their volatilization during decomposition, and the covalent interaction between nanoparticles and PP chains, which will also reduce the breakage of PP backbone chains.     

Cellular interactions of lauric acid and dextran-coated magnetite nanoparticles

In vitro cytocompatibility and cellular interactions of lauric acid and dextran-coated magnetite nanoparticles were evaluated with two different cell lines (mouse fibroblast and human cervical carcinoma). Lauric acid-coated magnetite nanoparticles were less cytocompatible than dextran-coated magnetite nanoparticles and cellular uptake of lauric acid-coated magnetic nanoparticles was more than that of dextran-coated magnetite nanoparticles. Lesser cytocompatibility and higher uptake of lauric acid-coated magnetite nanoparticles as compared to dextran-coated magnetic nanoparticles may be due to different cellular interactions by coating material. Thus, coating plays an important role in modulation of biocompatibility and cellular interaction of magnetic nanoparticles.